JPH04286608A - Method of molding artificial marble - Google Patents
Method of molding artificial marbleInfo
- Publication number
- JPH04286608A JPH04286608A JP7692491A JP7692491A JPH04286608A JP H04286608 A JPH04286608 A JP H04286608A JP 7692491 A JP7692491 A JP 7692491A JP 7692491 A JP7692491 A JP 7692491A JP H04286608 A JPH04286608 A JP H04286608A
- Authority
- JP
- Japan
- Prior art keywords
- molding material
- molding
- artificial marble
- mold
- radically polymerizable
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000000034 method Methods 0.000 title claims abstract description 44
- 238000000465 moulding Methods 0.000 title claims abstract description 23
- 239000002928 artificial marble Substances 0.000 title claims abstract description 16
- 239000012778 molding material Substances 0.000 claims abstract description 71
- 238000010526 radical polymerization reaction Methods 0.000 claims abstract description 16
- 238000001879 gelation Methods 0.000 claims abstract description 7
- 230000008602 contraction Effects 0.000 claims abstract description 4
- 238000002347 injection Methods 0.000 claims description 19
- 239000007924 injection Substances 0.000 claims description 19
- 239000000178 monomer Substances 0.000 claims description 16
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 claims description 15
- 229920005989 resin Polymers 0.000 claims description 8
- 239000011347 resin Substances 0.000 claims description 8
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 7
- 239000000945 filler Substances 0.000 claims description 6
- 239000007788 liquid Substances 0.000 claims description 6
- 229920005992 thermoplastic resin Polymers 0.000 claims description 6
- 229920001187 thermosetting polymer Polymers 0.000 claims description 6
- 238000005266 casting Methods 0.000 claims description 5
- 239000000203 mixture Substances 0.000 claims description 5
- 229920003229 poly(methyl methacrylate) Polymers 0.000 claims description 4
- 239000004926 polymethyl methacrylate Substances 0.000 claims description 4
- 229920006337 unsaturated polyester resin Polymers 0.000 claims description 4
- 229920001567 vinyl ester resin Polymers 0.000 claims description 4
- 239000006188 syrup Substances 0.000 claims description 3
- 235000020357 syrup Nutrition 0.000 claims description 3
- 230000002250 progressing effect Effects 0.000 claims description 2
- 238000002156 mixing Methods 0.000 claims 1
- 238000003825 pressing Methods 0.000 abstract description 3
- 238000000926 separation method Methods 0.000 abstract description 3
- 230000000694 effects Effects 0.000 description 7
- 238000010586 diagram Methods 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 4
- WNROFYMDJYEPJX-UHFFFAOYSA-K aluminium hydroxide Chemical compound [OH-].[OH-].[OH-].[Al+3] WNROFYMDJYEPJX-UHFFFAOYSA-K 0.000 description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 3
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 238000012856 packing Methods 0.000 description 3
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 2
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 2
- 150000001252 acrylic acid derivatives Chemical class 0.000 description 2
- IISBACLAFKSPIT-UHFFFAOYSA-N bisphenol A Chemical compound C=1C=C(O)C=CC=1C(C)(C)C1=CC=C(O)C=C1 IISBACLAFKSPIT-UHFFFAOYSA-N 0.000 description 2
- 230000002542 deteriorative effect Effects 0.000 description 2
- DOIRQSBPFJWKBE-UHFFFAOYSA-N dibutyl phthalate Chemical compound CCCCOC(=O)C1=CC=CC=C1C(=O)OCCCC DOIRQSBPFJWKBE-UHFFFAOYSA-N 0.000 description 2
- 238000001704 evaporation Methods 0.000 description 2
- -1 meth)acrylates Chemical class 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 2
- TXBCBTDQIULDIA-UHFFFAOYSA-N 2-[[3-hydroxy-2,2-bis(hydroxymethyl)propoxy]methyl]-2-(hydroxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC(CO)(CO)CO TXBCBTDQIULDIA-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- JLBJTVDPSNHSKJ-UHFFFAOYSA-N 4-Methylstyrene Chemical compound CC1=CC=C(C=C)C=C1 JLBJTVDPSNHSKJ-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 239000005062 Polybutadiene Substances 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- ZJCCRDAZUWHFQH-UHFFFAOYSA-N Trimethylolpropane Chemical compound CCC(CO)(CO)CO ZJCCRDAZUWHFQH-UHFFFAOYSA-N 0.000 description 1
- OKKRPWIIYQTPQF-UHFFFAOYSA-N Trimethylolpropane trimethacrylate Chemical compound CC(=C)C(=O)OCC(CC)(COC(=O)C(C)=C)COC(=O)C(C)=C OKKRPWIIYQTPQF-UHFFFAOYSA-N 0.000 description 1
- 230000002159 abnormal effect Effects 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 150000007513 acids Chemical class 0.000 description 1
- XYLMUPLGERFSHI-UHFFFAOYSA-N alpha-Methylstyrene Chemical compound CC(=C)C1=CC=CC=C1 XYLMUPLGERFSHI-UHFFFAOYSA-N 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000019 calcium carbonate Inorganic materials 0.000 description 1
- AXCZMVOFGPJBDE-UHFFFAOYSA-L calcium dihydroxide Chemical compound [OH-].[OH-].[Ca+2] AXCZMVOFGPJBDE-UHFFFAOYSA-L 0.000 description 1
- 239000000920 calcium hydroxide Substances 0.000 description 1
- 229910001861 calcium hydroxide Inorganic materials 0.000 description 1
- 239000000378 calcium silicate Substances 0.000 description 1
- 229910052918 calcium silicate Inorganic materials 0.000 description 1
- OYACROKNLOSFPA-UHFFFAOYSA-N calcium;dioxido(oxo)silane Chemical compound [Ca+2].[O-][Si]([O-])=O OYACROKNLOSFPA-UHFFFAOYSA-N 0.000 description 1
- 239000004927 clay Substances 0.000 description 1
- 229910052570 clay Inorganic materials 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- XRPZVNIXPWZPCA-UHFFFAOYSA-N ethenyl acetate;styrene Chemical compound CC(=O)OC=C.C=CC1=CC=CC=C1 XRPZVNIXPWZPCA-UHFFFAOYSA-N 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 239000012530 fluid Substances 0.000 description 1
- 239000006260 foam Substances 0.000 description 1
- 238000005187 foaming Methods 0.000 description 1
- 239000000499 gel Substances 0.000 description 1
- 235000011187 glycerol Nutrition 0.000 description 1
- 150000002334 glycols Chemical class 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 230000001771 impaired effect Effects 0.000 description 1
- 125000000959 isobutyl group Chemical group [H]C([H])([H])C([H])(C([H])([H])[H])C([H])([H])* 0.000 description 1
- 125000001449 isopropyl group Chemical group [H]C([H])([H])C([H])(*)C([H])([H])[H] 0.000 description 1
- VTHJTEIRLNZDEV-UHFFFAOYSA-L magnesium dihydroxide Chemical compound [OH-].[OH-].[Mg+2] VTHJTEIRLNZDEV-UHFFFAOYSA-L 0.000 description 1
- 239000000347 magnesium hydroxide Substances 0.000 description 1
- 229910001862 magnesium hydroxide Inorganic materials 0.000 description 1
- 239000004579 marble Substances 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000006082 mold release agent Substances 0.000 description 1
- 125000004108 n-butyl group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])* 0.000 description 1
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 description 1
- 229940117969 neopentyl glycol Drugs 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 229920001228 polyisocyanate Polymers 0.000 description 1
- 239000005056 polyisocyanate Substances 0.000 description 1
- 238000006116 polymerization reaction Methods 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000004814 polyurethane Substances 0.000 description 1
- 229920002635 polyurethane Polymers 0.000 description 1
- 229920002689 polyvinyl acetate Polymers 0.000 description 1
- 239000011118 polyvinyl acetate Substances 0.000 description 1
- 230000002028 premature Effects 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 229920006395 saturated elastomer Polymers 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 239000000454 talc Substances 0.000 description 1
- 229910052623 talc Inorganic materials 0.000 description 1
- 229920006305 unsaturated polyester Polymers 0.000 description 1
Landscapes
- Casting Or Compression Moulding Of Plastics Or The Like (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】本発明は天然大理石調の外観を有
する人工大理石を、常温または加温条件下で注型して硬
化させる人工大理石の成形方法に関するものである。BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for molding artificial marble, in which artificial marble having an appearance similar to natural marble is cast and cured at room temperature or under heated conditions.
【０００２】0002
【従来の技術】ラジカル重合性熱硬化性樹脂を主成分と
する成形材料を常温または加温条件下で注型して人工大
理石を成形する方法は、設備が簡単で比較的複雑な形状
のもので成形できることから広く一般に行われている。
しかしながら、ラジカル重合性成分を含む成形材料をこ
のような注型法によって硬化させると、ラジカル重合に
ともなう硬化収縮によって成形材料の体積が減少し、そ
のために硬化成形品の表面が型面より剥離し、次に述べ
る様な種々の欠陥を生じる。即ちこのような剥離が早期
に生じると、（１） 剥離を生じた面より未反応のモノ
マーが蒸発してしまい、表面の平滑性や色調を劣化させ
たり、あるいは（２）剥離が早く進行した部分と他の部
分の境界部に縞模様が形成されて外観を悪くし、更には
（３） 剥離によって生じた空間に未反応の液状成分が
流入してきて硬化し、表面に硬化物が付着したような異
常な外観を形成すること等がある。[Prior Art] A method of molding artificial marble by casting a molding material whose main component is a radically polymerizable thermosetting resin at room temperature or under heated conditions requires simple equipment and can be used for relatively complex shapes. It is widely used because it can be molded with. However, when a molding material containing a radically polymerizable component is cured by such a casting method, the volume of the molding material decreases due to curing shrinkage due to radical polymerization, which causes the surface of the cured molded product to peel off from the mold surface. , various defects as described below occur. In other words, if such peeling occurs early, (1) unreacted monomer evaporates from the surface where the peeling occurred, deteriorating the surface smoothness and color tone, or (2) peeling progresses quickly. A striped pattern is formed at the boundary between one part and another part, worsening the appearance, and (3) unreacted liquid components flow into the space created by peeling and harden, resulting in a cured product adhering to the surface. This may lead to the formation of an abnormal appearance.
【０００３】このような問題を解決する方法の一つとし
て、熱可塑性樹脂より成る低収縮化剤を成形材料に添加
して硬化時の体積収縮を抑制することが行われている。
しかしながらこのような方法は、硬化時に熱可塑性樹脂
が層分離して発泡することにより全体としての体積減少
を補おうとするものであるので、成形品は不透明な白濁
した外観となると共に、小さな気泡状の空間を多く含む
ため耐汚染性が悪くなってしまう。そのため大理石調の
透明感のある外観や、高い耐汚染性などが要求される人
工大理石の用途には使用し難いという問題がある。One method for solving these problems is to add a low-shrinkage agent made of a thermoplastic resin to the molding material to suppress volumetric shrinkage during curing. However, in this method, the thermoplastic resin layer separates and foams during curing to compensate for the overall volume loss, resulting in the molded product having an opaque, cloudy appearance and small bubble-like appearance. Contamination resistance deteriorates because it contains a large amount of space. Therefore, there is a problem that it is difficult to use it for artificial marble purposes, which require a marble-like transparent appearance and high stain resistance.
【０００４】一方前記した収縮の問題を解決する他の方
法として、成形材料を型内に注入した後に注入口を閉じ
、上型と下型を加圧して下型と上型の間に形成されるキ
ャビティ空間部を小さくするように圧力を加えて、硬化
成形品が型面から剥離するのを防止する方法が行われて
いる。On the other hand, as another method to solve the problem of shrinkage mentioned above, after the molding material is injected into the mold, the injection port is closed, and the upper mold and the lower mold are pressurized to form a mold between the lower mold and the upper mold. A method is used to prevent the cured molded product from peeling off from the mold surface by applying pressure to reduce the size of the cavity space.
【０００５】しかしながらこの方法においては、加圧の
ためにキャビティ空間部を減少していけるように、上型
と下型の構成を、たとえばプレス成形用の金型で用いら
れるような高精度の嵌合構造とする必要があったり、あ
るいは十分な加圧力を得るために大型の加圧装置が必要
であったりするため、型と型締め装置の双方に複雑で精
度の高い装置を必要とし、注型成形法の本来の特徴であ
る簡便性が損なわれることになり、好ましいものではな
かった。However, in this method, in order to reduce the cavity space for pressurization, the configuration of the upper mold and lower mold is made by using a high-precision fitting, such as that used in a press molding mold. Because it is necessary to have a joint structure or a large pressurizing device is necessary to obtain sufficient pressurizing force, complex and highly accurate devices are required for both the mold and the mold clamping device. This was not preferable because the simplicity, which is an original feature of the molding method, was impaired.
【０００６】[0006]
【発明が解決しようとする課題】本発明の目的は、成形
材料が早期に型面より剥離することによって生じる上記
欠点を、簡単な設備・装置であっても十分に解消するこ
とのできる方法を提供しようとするものであり、注型法
で用いられる型をそのまま用いることができ、成形材料
を型内に注入した後で成形材料に圧力を加え続けること
により、硬化物の早期剥離を防止する方法を提供しよう
とするものである。SUMMARY OF THE INVENTION An object of the present invention is to provide a method that can sufficiently eliminate the above-mentioned drawbacks caused by premature peeling of molding material from the mold surface, even with simple equipment and equipment. The mold used in the casting method can be used as is, and by continuing to apply pressure to the molding material after it is injected into the mold, it prevents the cured product from peeling off prematurely. It is intended to provide a method.
【０００７】[0007]
【課題を解決するための手段】上記目的を達成した本発
明は、上型と下型で形成されるキャビティ空間内に、常
温または加温条件下でラジカル重合して硬化する成形材
料を注入して硬化せしめ、所望形状の硬化物を得る注型
成形法において、前記キャビティ空間に成形材料を注入
したのちに、ラジカル重合が開始してゲル化には至って
いないが体積の収縮が進行している期間に、成形材料を
加圧して補充しつつラジカル重合を進行せしめ、ラジカ
ル重合が完了した後に脱型することを要旨とするもので
ある。[Means for Solving the Problems] The present invention achieves the above object by injecting a molding material that radically polymerizes and hardens at room temperature or under heated conditions into a cavity space formed by an upper mold and a lower mold. In the cast molding method, which obtains a cured product in the desired shape, radical polymerization begins after the molding material is injected into the cavity space, and although gelation has not yet occurred, volumetric contraction is proceeding. The gist of this method is to allow radical polymerization to proceed while pressurizing and replenishing the molding material during the molding period, and to remove the mold after the radical polymerization is completed.
【０００８】[0008]
【作用】本発明は、上型と下型で形成されるキャビティ
空間に、常温または加温条件下でラジカル重合して硬化
する成形材料を注入して硬化せしめ、所望の形状の硬化
物を得る注型成形法において、前記キャビティ空間に成
形材料を注入したのちに、キャビティ空間容積を変更す
ることなくキャビティ内の成形材料に対して圧力を加え
続けながら加圧下にラジカル重合を進行せしめるもので
あり、これによって成形材料を型面へ押し付ける様にし
て重合進行中の型離れを抑制し、成形品表面の形状を向
上させることができる。[Operation] In the present invention, a molding material that undergoes radical polymerization and hardens at room temperature or under heated conditions is injected into the cavity space formed by the upper mold and the lower mold and hardened, thereby obtaining a cured product in the desired shape. In the cast molding method, after the molding material is injected into the cavity space, radical polymerization is allowed to proceed under pressure while continuing to apply pressure to the molding material within the cavity without changing the volume of the cavity space. This allows the molding material to be pressed against the mold surface, suppressing mold separation during polymerization and improving the shape of the molded product surface.
【０００９】本発明に用いられる成形材料は、常温また
は加温条件下でラジカル重合により硬化する成形材料で
あれば特に制限されるものではないが、なかでも、１分
子中に２個以上のラジカル重合性基を有する多官能ラジ
カル重合性単量体と、該ラジカル重合性単量体と共重合
可能で、１分子中に１個のラジカル重合性基を有する単
官能ラジカル重合性単量体との混合物からなる熱硬化性
樹脂に充填剤を配合したもの、及び更に所望により熱可
塑性樹脂を混合せしめて成る成形材料を用いた場合は、
成形材料を加圧して型面よりの剥離を防止する本発明の
効果が一層現れ易く特に望ましいものとなる。[0009] The molding material used in the present invention is not particularly limited as long as it is a molding material that hardens by radical polymerization at room temperature or under heated conditions. A polyfunctional radically polymerizable monomer having a polymerizable group; a monofunctional radically polymerizable monomer that is copolymerizable with the radically polymerizable monomer and has one radically polymerizable group in one molecule; When using a molding material made of a thermosetting resin mixed with a filler, and further mixed with a thermoplastic resin if desired,
The effect of the present invention, which pressurizes the molding material to prevent it from peeling off from the mold surface, is more likely to appear and is particularly desirable.
【００１０】本発明によれば、ラジカル重合がスタート
して未だゲル化には至っていないが体積の収縮は進行し
ている期間に成形材料を補充して型からの剥離を防止す
る第１の効果、及び上型又は下型が薄肉厚のもので形成
される場合はゲル化に至るまでの期間に加えられた圧力
により上記薄肉厚の型を変形させておき、成形材料の収
縮が始まった時点で型の変形が回復することで硬化成形
品の剥離を防止する第２の効果がある。According to the present invention, the first effect is to prevent peeling from the mold by replenishing the molding material during a period when radical polymerization has started and gelation has not yet occurred but volumetric contraction is progressing. , and if the upper mold or lower mold is formed with a thin wall, the thin mold is deformed by pressure applied during the period up to gelation, and when the molding material begins to shrink. The second effect of preventing the cured molded product from peeling is achieved by recovering the deformation of the mold.
【００１１】したがって、第１の効果を発揮させるため
には、ラジカル重合が進行して体積収縮がかなり進行し
た後にゲル化にいたるような成形材料を使用することが
望ましい。すなわち多官能ラジカル重合性単量体と単官
能ラジカル重合性単量体との混合物からなる熱硬化性樹
脂に充填剤を配合して成る成形材料を用いた場合は、ラ
ジカル重合とゲル化の進行のタイミングが、上記第１の
効果を発揮する上で特に好ましいタイミングとなるため
である。[0011] Therefore, in order to exhibit the first effect, it is desirable to use a molding material that undergoes radical polymerization and undergoes considerable volumetric shrinkage before gelation occurs. In other words, when using a molding material made of a thermosetting resin made of a mixture of a polyfunctional radically polymerizable monomer and a monofunctional radically polymerizable monomer and a filler added thereto, radical polymerization and gelation progress. This is because the timing is particularly preferable for achieving the first effect.
【００１２】本発明に用いられる、１分子中に２個以上
のラジカル重合性基を有する多官能ラジカル重合性単量
体としては、たとえばエチレングリコール（メタ）アク
リレート、プロピレングリコール（メタ）アクリレート
、ネオペンチルグリコール（メタ）アクリレート、グリ
セリントリ（メタ）アクリレート、トリメチロールプロ
パントリ（メタ）アクリレート、ジペンタエリスリトー
ルヘキサ（メタ）アクリレート、ビスフェノールＡジ（
メタ）アクリレート等の多官能（メタ）アクリレートや
、ポリイソシアネート化合物にアクリル酸を反応させて
得られる不飽和ポリウレタン化合物、不飽和酸とグリコ
ールを縮合して得られる不飽和ポリエステル、ポリエポ
キシ化合物に（メタ）アクリル酸を反応させて得られる
ビニルエステル等を挙げることができる。Examples of the polyfunctional radically polymerizable monomer having two or more radically polymerizable groups in one molecule used in the present invention include ethylene glycol (meth)acrylate, propylene glycol (meth)acrylate, neo Pentyl glycol (meth)acrylate, glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, dipentaerythritol hexa(meth)acrylate, bisphenol A di(
Polyfunctional (meth)acrylates such as meth)acrylates, unsaturated polyurethane compounds obtained by reacting polyisocyanate compounds with acrylic acid, unsaturated polyesters obtained by condensing unsaturated acids and glycols, and polyepoxy compounds ( Examples include vinyl esters obtained by reacting meth)acrylic acid.
【００１３】本発明に用いられる単官能ラジカル重合性
単量体としては、たとえば、（メタ）アクリル酸、メチ
ル（メタ）アクリレート、エチル（メタ）アクリレート
、イソプロピル（メタ）アクリレート、イソブチル（メ
タ）アクリレート、ｎ−ブチル（メタ）アクリレート、
２−エチルヘキシル（メタ）アクリレート、ヒドロキシ
エチル（メタ）アクリレート等の（メタ）アクリル酸エ
ステル、スチレン、α−メチルスチレン、ｐ−メチルス
チレン等の芳香族ビニル化合物等を挙げることができる
。Examples of the monofunctional radically polymerizable monomer used in the present invention include (meth)acrylic acid, methyl (meth)acrylate, ethyl (meth)acrylate, isopropyl (meth)acrylate, and isobutyl (meth)acrylate. , n-butyl (meth)acrylate,
Examples include (meth)acrylic acid esters such as 2-ethylhexyl (meth)acrylate and hydroxyethyl (meth)acrylate, and aromatic vinyl compounds such as styrene, α-methylstyrene, and p-methylstyrene.
【００１４】また、本発明に用いられる充填剤は、一般
に当業界で用いられている無機質の粉体であり、たとえ
ば、炭酸カルシウム、タルク、クレー、シリカ、アルミ
ナ、石英、珪酸カルシウム等の粉体や、水酸化アルミニ
ウム、水酸化マグネシウム、水酸化カルシウム等の金属
酸化物の水和物を挙げることができる。[0014] The filler used in the present invention is an inorganic powder generally used in the art, such as powder of calcium carbonate, talc, clay, silica, alumina, quartz, calcium silicate, etc. and hydrates of metal oxides such as aluminum hydroxide, magnesium hydroxide, and calcium hydroxide.
【００１５】また、本発明に用いられる熱可塑性樹脂と
しては、たとえば、ポリメチルメタクリレート、ポリス
チレン、スチレン−酢酸ビニル系ポリマー、ポリ酢酸ビ
ニル、飽和ポリエステル、ポリブタジエンやイソプレン
系ポリマー等を挙げることができるが、これら熱可塑性
樹脂の使用量は、硬化時に層分離して発泡する事によっ
て人工大理石として必要な透明性や耐汚染性を損なうこ
とがないように、できるだけ少量の範囲で用いるように
する必要がある。なかでも、熱硬化性樹脂として、不飽
和ポリエステルおよび／またはビニルエステルに重合性
単量体を配合して成る不飽和ポリエステル樹脂および／
またはビニルエステル樹脂を用いた場合は型面からの剥
離が少なく、表面美麗な成形品が得られ易く望ましい。Examples of the thermoplastic resin used in the present invention include polymethyl methacrylate, polystyrene, styrene-vinyl acetate polymer, polyvinyl acetate, saturated polyester, polybutadiene, and isoprene polymer. The amount of these thermoplastic resins used must be as small as possible to avoid deteriorating the transparency and stain resistance necessary for artificial marble due to layer separation and foaming during curing. be. Among them, as thermosetting resins, unsaturated polyester resins and/or unsaturated polyester resins and/or vinyl esters blended with polymerizable monomers are used.
Alternatively, when a vinyl ester resin is used, it is desirable because there is little peeling from the mold surface and it is easy to obtain a molded product with a beautiful surface.
【００１６】また、多官能ラジカル重合性単量体として
多官能アクリレートを用いた場合は、硬化成形品の型面
からの剥離が少なく、美麗な成形品が得られ易い。また
、成形材料としてポリメチルメタクリレートをメチルメ
タクリレートモノマーに溶解させたメチルメタクリレー
トシラップに充填剤を配合したものを用いた場合は、硬
化物の型面からの剥離が少なく、美麗成形品が得られ望
ましい。Further, when a polyfunctional acrylate is used as the polyfunctional radically polymerizable monomer, peeling of the cured molded product from the mold surface is reduced, and a beautiful molded product is easily obtained. In addition, if a filler is used as a molding material in methyl methacrylate syrup, which is made by dissolving polymethyl methacrylate in methyl methacrylate monomer, the cured product will not peel off from the mold surface and a beautiful molded product will be obtained. .
【００１７】本発明は、上記のような成形材料を型内に
注入した後に、引き続き成形材料に圧力を加え続けるこ
とによって実施されるが、成形材料に圧力を加える方法
としては、たとえば以下のような方法をとることができ
る。The present invention is carried out by continuing to apply pressure to the molding material after injecting the molding material into the mold. Examples of methods for applying pressure to the molding material include, for example, as follows. method can be used.
【００１８】第１の方法は、成形材料を注入口より注入
した後に、引き続き注入口より成形材料を加圧して注入
し続けることにより行う方法で、成形材料の加圧は、少
なくとも成形材料がゲル化して完全に流動性を失うまで
は継続する必要がある。この方法においては、成形用の
型を加工する必要がなく、また特殊な装置を必要としな
い点で好ましい。The first method is to inject the molding material from the injection port and then pressurize the molding material from the injection port and continue to inject it. It is necessary to continue this process until it becomes liquid and loses liquidity completely. This method is preferable because it does not require processing of a mold and does not require any special equipment.
【００１９】第２の方法は、成形用型の一部にあらかじ
め成形材料を加圧するためのピストン機構を設けておき
、成形材料を注入した後に注入口を閉じ、ついで該ピス
トン機構を用いて成形材料に圧力を加える方法である。
この方法は簡単な装置を付加するだけで、効果的に成形
材料を加圧することができ、美麗な成形品を得ることが
できる。このようなピストン機構は、注入口と兼用する
ようなものであってもよく、或は別の部位に設けても良
い。ピストン機構は、円筒状のシリンダー部と、シリン
ダー内を実質的に成形材料の漏れがないようにシールし
た状態でスライドするように構成されたピストンと、該
ピストンを加圧するための手段からなるものである。In the second method, a piston mechanism for pressurizing the molding material is provided in advance in a part of the molding die, the injection port is closed after the molding material is injected, and then the piston mechanism is used to perform the molding. This method applies pressure to the material. With this method, by simply adding a simple device, the molding material can be effectively pressurized and a beautiful molded product can be obtained. Such a piston mechanism may also serve as an injection port, or may be provided at a different location. The piston mechanism consists of a cylindrical cylinder part, a piston configured to slide inside the cylinder in a sealed state to substantially prevent leakage of molding material, and means for pressurizing the piston. It is.
【００２０】第３の方法は、成形材料を型に注入した後
に注入口を閉じ、ついで該注入口または、型の一部に設
けられた別の加圧口より、硬化しない不活性液体を加圧
して注入し続ける方法であり、この場合は成形材料がゲ
ル化して流動性を失った後さらに収縮して型面から剥離
しようとする際硬化成形品と型との隙間に該液体が充填
されることになり、未反応重合性単量体の蒸発が防止さ
れる効果もある。The third method is to close the injection port after injecting the molding material into the mold, and then apply an inert liquid that does not harden through the injection port or another pressure port provided in a part of the mold. This is a method of continuously injecting under pressure, and in this case, after the molding material gels and loses its fluidity, it shrinks further and tries to peel off from the mold surface, and the liquid fills the gap between the hardened molded product and the mold. This also has the effect of preventing evaporation of unreacted polymerizable monomers.
【００２１】[0021]
【実施例】図１は本発明方法の一例を示す説明図であり
、ピストン５を使用した例である。すなわち雄型１と雌
型２の間に形成されるキャビティ３内に、注入口２Ａを
介して成形材料Ｐを充填し、該注入口２Ａ内で摺動自在
に嵌設されたピストン５によって前記成形材料Ｐを押圧
しつつ、成形材料の硬化を行なう。なお符号４はパッキ
ンを示し、型周縁より成形材料Ｐが漏出を防止するもの
である。DESCRIPTION OF THE PREFERRED EMBODIMENTS FIG. 1 is an explanatory diagram showing an example of the method of the present invention, in which a piston 5 is used. That is, the molding material P is filled into the cavity 3 formed between the male die 1 and the female die 2 through the injection port 2A, and the molding material P is filled with the molding material P through the injection port 2A. The molding material P is cured while being pressed. Note that the reference numeral 4 indicates a packing, which prevents the molding material P from leaking from the periphery of the mold.
【００２２】この様な方法であれば成形材料Ｐにおける
体積収縮を補充すると共に、雌型２は薄肉厚であるので
、この変形回復により、硬化成形品が雄型１及び雌型２
の型面から剥離することが防止され、表面が平滑で美麗
な成形品を得ることができる。With this method, the volume shrinkage in the molding material P is compensated for, and since the female mold 2 has a thin wall thickness, this deformation recovery causes the hardened molded product to form the male mold 1 and the female mold 2.
Peeling from the mold surface is prevented, and a beautiful molded product with a smooth surface can be obtained.
【００２３】図２は本発明の他の方法を示す説明図であ
り、下型１ａと上型２ａの間に形成されるキャビティ３
内に、注入口２Ａを介して成形材料Ｐを装填し、次いで
注入口２Ａの開口部は密閉蓋６によって閉塞すると共に
、該蓋に接続された供給管７を介して、硬化しない流体
として例えば加圧水Ｗを注入口２Ａ内に導入する。これ
によって成形材料Ｐは加圧水に押圧された状態で硬化が
進行すると共に、成形材料の収縮により型（１ａ、２ａ
）と硬化成形品との間に隙間が形成されることがあった
場合でも、加圧水Ｗが該隙間に速やかに進入して未反応
重合性単量体の蒸発を防止する。FIG. 2 is an explanatory diagram showing another method of the present invention, in which a cavity 3 formed between a lower mold 1a and an upper mold 2a is
The molding material P is loaded into the molding material P through the injection port 2A, and then the opening of the injection port 2A is closed by a sealing lid 6, and a non-hardening fluid, for example, is supplied through a supply pipe 7 connected to the lid. Pressurized water W is introduced into the injection port 2A. As a result, the molding material P is hardened while being pressed by the pressurized water, and the molds (1a, 2a
) and the cured molded product, the pressurized water W quickly enters the gap to prevent the unreacted polymerizable monomer from evaporating.
【００２４】（実施例１）不飽和ポリエステル樹脂［日
本触媒化学工業（株）社製；エポラックＭＲ−３００］
１００部、水酸化アルミニウム［昭和電工（株）社製；
ハイジライトＨ−３２０］２００部を混合したものに、
メチルエチルケトンパーオキサイド５５％、ジブチルフ
タレート溶液１部を添加し、よく混合して成形材料を得
た。ついで幅９００ｍｍ奥行き６５０ｍｍで厚さが１２
ｍｍのテーブルトップを成形する為の雌・雄一対の型表
面に離型剤を塗布した後、雌・雄型を組み合わせてクラ
ンプで固定し、注入口より上記成形材料を注入して内部
の空間を満たした。ついで注入口に、パイプを付加せし
めた栓をはめ込んで固定し、該パイプを通して水を加圧
して注入した。水の圧力は、０．７ｋｇ／ｃｍ２、６０
分間加圧して水を注入し続け、６０分後に脱型した。得
られた成形品の表面は平滑で、外観性状に優れたもので
あった。(Example 1) Unsaturated polyester resin [manufactured by Nippon Shokubai Chemical Co., Ltd.; Eporac MR-300]
100 parts, aluminum hydroxide [manufactured by Showa Denko Co., Ltd.;
Hygilite H-320] mixed with 200 parts,
55% methyl ethyl ketone peroxide and 1 part of dibutyl phthalate solution were added and mixed well to obtain a molding material. Next, the width is 900mm, the depth is 650mm, and the thickness is 12.
After applying a mold release agent to the surfaces of a pair of female and male molds for molding a mm table top, the female and male molds are combined and fixed with a clamp, and the above molding material is injected from the injection port to fill the internal space. fulfilled. Then, a plug to which a pipe was attached was fitted and fixed into the injection port, and water was injected under pressure through the pipe. The pressure of water is 0.7 kg/cm2, 60
Water was continued to be injected under pressure for a minute, and the mold was demolded after 60 minutes. The surface of the obtained molded product was smooth and had excellent appearance properties.
【００２５】（実施例２）メチルメタクリレート５０部
，スチレン３０部，トリメチロールプロパントリメタク
リレート２０部からなる混合物に実施例１で用いたもの
と同じ水酸化アルミニウム２５０部を混合してよく撹拌
し、さらに硬化剤（化薬アクゾ社製；カヤエステルＯ）
１部を添加して混合し、成形材料を得た。次に直径８０
０ｍｍ、高さ１０００ｍｍ、肉厚１５ｍｍの半円錐を成
形する図３に示す上下一対の型の片方の端部に注入口２
Ａを設けると共に、他端に成形材料を加圧するためのピ
ストン機構５Ａを設けたものによって成形を行なった。
注入口２Ａより成形材料Ｐを注入して型内部とピストン
機構５Ａのシリンダ内部を成形材料で満たした後にシリ
ンダにピストンを取付け、ピストンをネジとスプリング
で構成される加圧機構によって押し下げ、成形材料を加
圧した。この状態で型全体を７０℃の硬化炉に入れ２時
間放置して硬化した後、脱型した。この結果、得られた
成形品の表面は平滑で外観性状に優れたものであった。(Example 2) 250 parts of aluminum hydroxide, the same as that used in Example 1, was mixed with a mixture of 50 parts of methyl methacrylate, 30 parts of styrene, and 20 parts of trimethylolpropane trimethacrylate, and the mixture was thoroughly stirred. Furthermore, a hardening agent (manufactured by Kayaku Akzo; Kaya Ester O)
1 part was added and mixed to obtain a molding material. Next, the diameter is 80
An injection port 2 is installed at one end of a pair of upper and lower molds shown in Fig. 3, which are used to mold a semicone with a diameter of 0 mm, a height of 1000 mm, and a wall thickness of 15 mm.
A and a piston mechanism 5A for pressurizing the molding material at the other end were used for molding. After injecting the molding material P from the injection port 2A to fill the inside of the mold and the cylinder of the piston mechanism 5A with the molding material, a piston is attached to the cylinder, and the piston is pushed down by a pressure mechanism composed of a screw and a spring, and the molding material is filled. was pressurized. In this state, the entire mold was placed in a curing furnace at 70° C. and left to harden for 2 hours, and then removed from the mold. As a result, the surface of the molded product obtained was smooth and had excellent appearance.
【００２６】（実施例３）ポリメチルメタクリレート（
住友化学工業（株）製；スミペックスＢ）２０部を８０
部のメチルメタクリレートに溶解せしめたメチルメタク
リレートシラップ１００部に実施例１で用いたものと同
じ水酸化アルミニウム２００部を混合し、さらに硬化剤
（化薬アクゾ社製，カヤエステルＯ）１部を添加してよ
く撹拌し、成形材料Ｐを得た。次にサイドパッキンをス
ライドできるように構成した図４に示すテーブルトップ
成形用の上下型２ａ，１ａを７０℃に加温しておき、上
記成形材料Ｐを注入した後、サイドパッキン１１をエア
シリンダ１０によってスライドさせ成形材料Ｐを加圧し
た。この状態で６０分間保持し、その後脱型した。これ
により得られた成形品の表面は平滑で、外観性状に優れ
たものであった。(Example 3) Polymethyl methacrylate (
Sumitomo Chemical Co., Ltd.; Sumipex B) 20 parts to 80 parts
200 parts of aluminum hydroxide, the same as that used in Example 1, was mixed with 100 parts of methyl methacrylate syrup dissolved in 100 parts of methyl methacrylate, and 1 part of a hardening agent (Kaya Ester O, manufactured by Kayaku Akzo Co., Ltd.) was added. The mixture was thoroughly stirred to obtain a molding material P. Next, the upper and lower molds 2a and 1a for table top molding shown in FIG. 4, which are configured so that the side packing can slide, are heated to 70°C, and after injecting the molding material P, the side packing 11 is placed in an air cylinder. 10 to pressurize the molding material P. This state was held for 60 minutes and then demolded. The surface of the molded product thus obtained was smooth and had excellent appearance properties.
【００２７】[0027]
【発明の効果】本発明は以上の様に構成されているので
、通常の注型法に用いられる型を活用する場合であって
も、成形材料が早期に型面より剥離するのを防止するこ
とができ、表面が平滑で美麗な成形品を製造できる様に
なった。[Effects of the Invention] Since the present invention is constructed as described above, even when using a mold used in a normal casting method, it is possible to prevent the molding material from prematurely peeling off from the mold surface. This has made it possible to produce molded products with smooth and beautiful surfaces.
【図１】本発明方法の一例を示す説明図である。FIG. 1 is an explanatory diagram showing an example of the method of the present invention.
【図２】本発明方法の他の例を示す説明図である。FIG. 2 is an explanatory diagram showing another example of the method of the present invention.
【図３】本発明方法の他の例を示す説明図である。FIG. 3 is an explanatory diagram showing another example of the method of the present invention.
【図４】本発明方法の他の例を示す説明図である。FIG. 4 is an explanatory diagram showing another example of the method of the present invention.
１ 雄型 ２ 雌型 ２Ａ 注入口 ３ キャビティ Ｐ 成形材料 1 Male type 2 Female type 2A Inlet 3 Cavity P Molding material
Claims (8)
間内に、常温または加温条件下でラジカル重合して硬化
する成形材料を注入して硬化せしめ、所望形状の硬化物
を得る注型成形法において、前記キャビティ空間に成形
材料を注入したのちに、ラジカル重合が開始してゲル化
には至っていないが体積の収縮が進行している期間に、
成形材料を加圧して補充しつつラジカル重合を進行せし
め、ラジカル重合が完了した後に脱型することを特徴と
する人工大理石の成形方法。1. A casting method in which a molding material that radically polymerizes and hardens at room temperature or under heated conditions is injected into a cavity space formed by an upper mold and a lower mold and hardened to obtain a cured product in a desired shape. In the molding method, after the molding material is injected into the cavity space, radical polymerization has started and gelation has not yet occurred, but volumetric contraction is progressing,
A method for molding artificial marble, characterized by allowing radical polymerization to proceed while pressurizing and replenishing a molding material, and removing the mold after the radical polymerization is completed.
ジカル重合性基を有する多官能ラジカル重合性単量体と
、該ラジカル重合性単量体と共重合可能で、１分子中に
１個のラジカル重合性基を有する単官能ラジカル重合性
単量体との混合物からなる熱硬化性樹脂、及び充填剤を
配合し、さらに熱可塑性樹脂を混合せしめて成るもので
ある請求項１記載の人工大理石の成形方法。2. The molding material is a polyfunctional radically polymerizable monomer having two or more radically polymerizable groups in one molecule, and is copolymerizable with the radically polymerizable monomer. Claim 1, wherein a thermosetting resin consisting of a mixture with a monofunctional radically polymerizable monomer having one radically polymerizable group and a filler are blended, and a thermoplastic resin is further mixed therein. How to form artificial marble.
樹脂および／またはビニルエステル樹脂である請求項２
記載の人工大理石の成形方法。[Claim 3] The thermosetting resin is an unsaturated polyester resin and/or a vinyl ester resin. [Claim 2]
The method of forming artificial marble described.
アクリレートである請求項２記載の人工大理石の成形方
法。4. The method for molding artificial marble according to claim 2, wherein the polyfunctional radically polymerizable monomer is a polyfunctional acrylate.
トをメチルメタクリレートモノマーに溶解させたメチル
メタクリレートシラップに充填剤を配合してなるもので
ある請求項１記載の人工大理石の成形方法。5. The method for molding artificial marble according to claim 1, wherein the molding material is made by blending a filler with methyl methacrylate syrup prepared by dissolving polymethyl methacrylate in a methyl methacrylate monomer.
未硬化の液状成形材料を加圧して注入し続けることによ
り行う請求項１記載の人工大理石の成形方法。6. The method for molding artificial marble according to claim 1, wherein the pressurization of the molding material is carried out by continuing to pressurize and inject uncured liquid molding material from a molding material injection port.
部に前記注入口とは別途に設けられたピストン機構によ
りキャビティ内の成形材料を加圧することにより行う請
求項１記載の人工大理石の成形方法。7. The molding material according to claim 1, wherein the molding material is pressurized by pressurizing the molding material in the cavity by a piston mechanism provided separately from the injection port in a part of the upper mold or the lower mold. How to form artificial marble.
部に前記注入口とは別途に設けられた加圧口より、未硬
化の液状成形材料を加圧注入することによって行なう請
求項１記載の人工大理石の成形方法。[Claim 8] The molding material is pressurized by injecting the uncured liquid molding material under pressure through a pressure port provided separately from the injection port in a part of the upper mold or the lower mold. The method for molding artificial marble according to claim 1.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7692491A JPH04286608A (en) | 1991-03-15 | 1991-03-15 | Method of molding artificial marble |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP7692491A JPH04286608A (en) | 1991-03-15 | 1991-03-15 | Method of molding artificial marble |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04286608A true JPH04286608A (en) | 1992-10-12 |
Family
ID=13619264
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP7692491A Pending JPH04286608A (en) | 1991-03-15 | 1991-03-15 | Method of molding artificial marble |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04286608A (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011153194A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Thermosetting resin molded product |
| JP2014156115A (en) * | 2013-01-16 | 2014-08-28 | Toray Ind Inc | Method of producing fiber-reinforced resin |
-
1991
- 1991-03-15 JP JP7692491A patent/JPH04286608A/en active Pending
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP2011153194A (en) * | 2010-01-26 | 2011-08-11 | Panasonic Electric Works Co Ltd | Thermosetting resin molded product |
| JP2014156115A (en) * | 2013-01-16 | 2014-08-28 | Toray Ind Inc | Method of producing fiber-reinforced resin |
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